CN110270377A - A kind of methane dry reforming nickel-base catalyst and its preparation method and application - Google Patents
A kind of methane dry reforming nickel-base catalyst and its preparation method and application Download PDFInfo
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- CN110270377A CN110270377A CN201910586784.3A CN201910586784A CN110270377A CN 110270377 A CN110270377 A CN 110270377A CN 201910586784 A CN201910586784 A CN 201910586784A CN 110270377 A CN110270377 A CN 110270377A
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- base catalyst
- nickel
- dry reforming
- methane dry
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- 239000003054 catalyst Substances 0.000 title claims abstract description 87
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 238000002407 reforming Methods 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 40
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 32
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 32
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 32
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 32
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 32
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims abstract description 24
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000004471 Glycine Substances 0.000 claims abstract description 13
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002245 particle Substances 0.000 claims abstract description 12
- 238000010792 warming Methods 0.000 claims abstract description 11
- 238000000227 grinding Methods 0.000 claims abstract description 10
- 239000004202 carbamide Substances 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 8
- 229960003512 nicotinic acid Drugs 0.000 claims abstract description 8
- 235000001968 nicotinic acid Nutrition 0.000 claims abstract description 8
- 239000011664 nicotinic acid Substances 0.000 claims abstract description 8
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000376 reactant Substances 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 238000010438 heat treatment Methods 0.000 claims description 7
- 230000003197 catalytic effect Effects 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000007873 sieving Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 2
- 238000003801 milling Methods 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
- 239000002253 acid Substances 0.000 claims 2
- 244000248349 Citrus limon Species 0.000 claims 1
- 235000005979 Citrus limon Nutrition 0.000 claims 1
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- 235000009508 confectionery Nutrition 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 39
- 229910002651 NO3 Inorganic materials 0.000 description 30
- 239000007789 gas Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000012216 screening Methods 0.000 description 8
- 238000005469 granulation Methods 0.000 description 7
- 230000003179 granulation Effects 0.000 description 7
- 230000009257 reactivity Effects 0.000 description 6
- 230000009467 reduction Effects 0.000 description 5
- 238000005245 sintering Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 229910052593 corundum Inorganic materials 0.000 description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 3
- 239000005431 greenhouse gas Substances 0.000 description 3
- 230000002779 inactivation Effects 0.000 description 3
- 229910000480 nickel oxide Inorganic materials 0.000 description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 3
- 238000006057 reforming reaction Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000006004 Quartz sand Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- XZWYZXLIPXDOLR-UHFFFAOYSA-N metformin Chemical compound CN(C)C(=N)NC(N)=N XZWYZXLIPXDOLR-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 210000002700 urine Anatomy 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- B01J35/50—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/847—Nickel
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0238—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a carbon dioxide reforming step
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention discloses a kind of preparation methods of methane dry reforming nickel-base catalyst, and this method includes: (1) by Ni (NO3)2·6H2O, complexant and SiO2Grinding, is fitted into air-tight bottle, reacts in 40~100 DEG C；(2) step (1) reactant is roasted, is warming up to 300~800 DEG C of roastings, be granulated, screen the particle of 40~60 mesh, obtain the nickel-base catalyst that Ni load capacity is 5%~20%.Wherein, any one of the complexant in citric acid, trimesic acid, urea, glycine and niacin；The complexant, Ni (NO3)2·6H2O and SiO2Molar ratio be 1~6:1:(3~20).Method of the invention has prepared the methane dry reforming preparing synthetic gas nickel-base catalyst of high activity and high stability, and preparation method is simple, it is easy to accomplish industrialization, and reduce catalyst cost of manufacture.
Description
Technical field
The present invention relates to a kind of nickel-base catalysts, and in particular to a kind of methane dry reforming nickel-base catalyst and preparation method thereof
And purposes.
Background technique
As people go deep into greenhouse effects understanding, the CO as most one of strong greenhouse gas2Capture and its effectively
Using causing increasingly extensive attention.Wherein, CO2With the cleaning of natural gas or coal bed gas (main component is methane), utilize
The CH combined4Dry reforming (DRM) preparing synthetic gas technology has been a great concern.DRM process in addition to utilizing CO simultaneously2And CH4
Two big greenhouse gases, except being of great significance to reduction of greenhouse gas discharge, the H of the synthesis gas of production2/ CO≤1, can be used as carbonyl
The unstripped gas of long-chain hydro carbons is synthesized and synthesized through Fischer-Tropsch (FT) synthetic reaction with organic oxygen-containing compound.Importantly, with
Other CO2Trans-utilization technology is compared, and DRM is expected to directly apply to CH4With CO in flue gas2Reforming reaction, without to cigarette
CO in road gas2Carry out pre-separation.Therefore, accelerate the process of industrialization of DRM reaction for realizing CO2Emission reduction and efficient utilize have
Significant application value.Studies have shown that catalyst inactivation caused by carbon deposit and sintering is the bottleneck of DRM industrial applications.Therefore, it encloses
Stability around catalyst has carried out numerous studies.
Although the catalytic activity such as precious metals pt, Rh and coking resistivity are substantially better than Ni, comprehensively consider catalytic performance and
Economy, Ni base catalyst are optimal.Therefore, it is necessary to study the catalytic performance for improving Ni base catalyst in DRM reaction.
Summary of the invention
The object of the present invention is to provide a kind of methane dry reforming nickel-base catalyst and its preparation method and application, the catalyst
Existing catalyst is solved the problems, such as easily because carbon deposit and sintering cause inactivation, this method has prepared high activity and high stability
Methane dry reforming preparing synthetic gas nickel-base catalyst, preparation method are simple, it is easy to accomplish industrialization, and reduce catalyst and be fabricated to
This.
In order to achieve the above object, the present invention provides a kind of preparation method of methane dry reforming nickel-base catalyst, the party
Method includes:
(1) by Ni (NO3)2·6H2O, complexant and SiO2Grinding, is fitted into air-tight bottle, reacts in 40~100 DEG C；
(2) step (1) reactant is roasted, is warming up to 300~800 DEG C of roastings, be granulated, screen 40~60 purposes
Grain obtains the nickel-base catalyst that Ni load capacity is 5%~20%.
Wherein, any one of the complexant in citric acid, trimesic acid, urea, glycine and niacin；Institute
State complexant, Ni (NO3)2·6H2O and SiO2Molar ratio be 1~6:1:(3~20).
Preferably, in step (1), the milling time is 30min.
Preferably, in step (1), the reaction time is 10~48h.
Preferably, in step (2), the calcining time is 3~5h.
Preferably, in step (2), the heating rate is 5 DEG C/min.
The present invention also provides a kind of methane dry reforming nickel-base catalyst, which is by Ni (NO3)2·6H2O, match
Position agent and SiO2Cross what 40~60 meshes obtained after grinding, sealing 40~100 DEG C of heating reactions, 300~800 DEG C of roastings；
Wherein, any one of the complexant in citric acid, trimesic acid, urea, glycine and niacin；The coordination
Agent, Ni (NO3)2·6H2O and SiO2Molar ratio be 1~6:1:(3~20)；In the nickel-base catalyst Ni load capacity be 5%~
20%.
Catalyst of the invention has XRD characterization shown in embodiment 1 as shown in figure 1, also has such as 1 institute of embodiment in Fig. 2
The TPR table sign shown.
Preferably, which obtains through the preparation method of the methane dry reforming nickel-base catalyst.
Preferably, which is by Ni (NO3)2·6H2O, citric acid and SiO2Reacted by grinding, heated sealed,
Sieving obtains after roasting；Wherein, the citric acid, Ni (NO3)2·6H2O and SiO2Molar ratio be 2:1:8~9.
Preferably, which is by Ni (NO3)2·6H2O, glycine and SiO2Reacted by grinding, heated sealed,
Sieving obtains after roasting；Wherein, the glycine, Ni (NO3)2·6H2O and SiO2Molar ratio be 4:1:8~9.
The present invention also provides the purposes of the methane dry reforming nickel-base catalyst described in one kind, the catalyst is dry for methane
The catalysis of reforming reaction restores.
Methane dry reforming nickel-base catalyst of the invention and its preparation method and application solves existing catalyst Yi Yinji
Charcoal and sintering cause the problem of inactivation, have the advantage that
(1) nickel-base catalyst of the invention is the presoma of Ni, citric acid, trimesic acid, urine with Nickelous nitrate hexahydrate
Element, glycine or niacin are complexant, SiO2For carrier, the methane dry reforming system synthesis of high activity and high stability has been prepared
Gas nickel-base catalyst, preparation method are simple, it is easy to accomplish industrialization, and reduce catalyst cost of manufacture；
(2) nickel-base catalyst of the invention, avoids carbon deposit and sintering, not only shows higher reactivity (CH4With
CO2Conversion ratio), CH4And CO2Conversion ratio be respectively higher than 81% and 90%, while excellent stability is shown, after reacting 20h
Conversion ratio is held essentially constant, or even after reaction 100 hours, conversion ratio is held essentially constant；
(3) preparation method of the invention is matched compared with traditional equi-volume impregnating and being simply mixed using of the invention
The catalyst of position-polishing preparation can significantly improve methane dry reforming reactivity worth, especially stability；
(4) preparation method of the invention is simply easily operated, and complexant used is cheap and easy to get, and reproducible.
Detailed description of the invention
Fig. 1 is the XRD characterization of nickel-base catalyst prepared by embodiment 1 and comparative example 1.
Fig. 2 is the TPR table sign of nickel-base catalyst prepared by embodiment 1 and comparative example 1.
Fig. 3 is nickel-base catalyst CH prepared by embodiment 14With CO2Conversion ratio with the reaction time change curve.
Specific embodiment
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation
Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is common
Technical staff's every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.
Embodiment 1
A kind of preparation method of methane dry reforming nickel-base catalyst includes:
It (1) is 10% according to W metal load capacity, by 0.55g Ni (NO3)2·6H2(0.0019mol, molecular weight are O
290.81g/mol), 0.80g citric acid (0.0038mol, C6H8O7·H2O, molecular weight 210.14g/mol) (complexant and Ni
(NO3)2·6H2The molar ratio of O is 2:1) and 1.00g SiO2(0.017mol, molecular weight 60.084g/mol) (SiO2With Ni
(NO3)2·6H2The molar ratio of O is 9:1) it is put into mortar, it is fully ground 30min, is then charged into air-tight bottle, 80 DEG C of reactions
24h；
(2) step (1) reactant is moved into crucible, 500 DEG C of roasting 4h is risen to the heating rate of 5 DEG C/min, tabletting,
It is granulated, the particle of 40~60 mesh of screening, obtains 10%Ni- citric acid/SiO2Catalyst.
Comparative example 1
Substantially the same manner as Example 1, difference is: not adding citric acid, obtains 10%Ni/SiO2Catalyst.
As shown in Figure 1, the XRD characterization of the nickel-base catalyst prepared for embodiment 1 and comparative example 1, as seen from Figure 1,
For the diffraction peak intensity of catalyst prepared by embodiment 1 significantly lower than comparative example 1, corresponding half-peak breadth is also obvious wider, these
Illustrate that the particle size of the nickel oxide on the nickel-base catalyst of the preparation of embodiment 1 is smaller, to alleviate carbon deposit, this is also explained
There is the reason of preferable DRM reactivity and stability.
As shown in Fig. 2, the TPR table sign of the nickel-base catalyst prepared for embodiment 1 and comparative example 1, as seen from Figure 2,
Compared with comparative example 1, catalyst prepared by embodiment 1 in addition to other than 400 DEG C of reduction peak, 450~600 DEG C of high temperature there is also
One apparent reduction peak shows the more difficult reduction of nickel oxide on the catalyst of the preparation of embodiment 1, this illustrates prepared by embodiment 1
Catalyst on nickel oxide and carrier have compared with strong interaction, so that the sintering of nickel particle is inhibited, to extend catalysis
The service life of agent.
Embodiment 2
A kind of preparation method of methane dry reforming nickel-base catalyst, substantially the same manner as Example 1, difference is:
In step (1), Ni (NO3)2·6H2O dosage is 0.26g (0.00089mol, molecular weight 290.81g/mol),
Urea (0.0053mol, molecular weight 60.06g/mol) dosage is 0.32g, i.e. complexant and Ni (NO3)2·6H2The molar ratio of O
For 6:1, SiO2With Ni (NO3)2·6H2The molar ratio of O is 19:1；40 DEG C of reaction 12h in air-tight bottle；
In step (2), 700 DEG C of roasting 3h are warming up to, tabletting, granulation, the particle for screening 40~60 mesh obtain 5%Ni-
Urea/SiO2Catalyst.
Embodiment 3
A kind of preparation method of methane dry reforming nickel-base catalyst, substantially the same manner as Example 1, difference is:
In step (1), Ni (NO3)2·6H2O dosage is 0.87g (0.0030mol, molecular weight 290.81g/mol),
Glycine (molecular weight 75.07g/mol) dosage is 0.45g, i.e. complexant and Ni (NO3)2·6H2The molar ratio of O is 2:1,
SiO2With Ni (NO3)2·6H2The molar ratio of O is 6:1；100 DEG C of reaction 12h in air-tight bottle；
In step (2), 600 DEG C of roasting 4h are warming up to, tabletting, granulation, the particle for screening 40~60 mesh obtain 15%
Ni- glycine/SiO2Catalyst.
Embodiment 4
A kind of preparation method of methane dry reforming nickel-base catalyst, substantially the same manner as Example 1, difference is:
In step (1), Ni (NO3)2·6H2O dosage is 0.26g (0.00089mol, molecular weight 290.81g/mol),
Niacin (molecular weight 123.11g/mol) dosage is 0.55g, i.e. complexant and Ni (NO3)2·6H2The molar ratio of O is 5:1,
SiO2With Ni (NO3)2·6H2The molar ratio of O is 19:1；50 DEG C of reaction 36h in air-tight bottle；
In step (2), 800 DEG C of roasting 3h are warming up to, tabletting, granulation, the particle for screening 40~60 mesh obtain 5%Ni-
Niacin/SiO2Catalyst.
Embodiment 5
A kind of preparation method of methane dry reforming nickel-base catalyst, substantially the same manner as Example 1, difference is:
In step (1), Ni (NO3)2·6H2O dosage is 0.87g (0.0030mol, molecular weight 290.81g/mol),
Trimesic acid (molecular weight 210.14g/mol) dosage is 0.63g, i.e. complexant and Ni (NO3)2·6H2The molar ratio of O is
1:1, SiO2With Ni (NO3)2·6H2The molar ratio of O is 6:1；It is reacted for 24 hours for 90 DEG C in air-tight bottle；
In step (2), 400 DEG C of roasting 5h are warming up to, tabletting, granulation, the particle for screening 40~60 mesh obtain 15%
Ni- trimesic acid/Al2O3Catalyst.
Embodiment 6
A kind of preparation method of methane dry reforming nickel-base catalyst, substantially the same manner as Example 1, difference is:
In step (1), Ni (NO3)2·6H2O dosage is 1.24g (0.0043mol, molecular weight 290.81g/mol),
Amount of urea is 0.77g, i.e. complexant and Ni (NO3)2·6H2The molar ratio of O is 3:1, SiO2With Ni (NO3)2·6H2O's rubs
You are than being 4:1；70 DEG C of reaction 48h in air-tight bottle；
In step (2), 500 DEG C of roasting 5h are warming up to, tabletting, granulation, the particle for screening 40~60 mesh obtain 20%
Ni- urea/Al2O3Catalyst.
Embodiment 7
A kind of preparation method of methane dry reforming nickel-base catalyst, substantially the same manner as Example 1, difference is:
In step (1), glycine dosage is 0.57g, i.e. complexant and Ni (NO3)2·6H2The molar ratio of O is 4:1；It is close
Seal 70 DEG C of reaction 48h in bottle；70 DEG C of reaction 12h in air-tight bottle；
In step (2), 600 DEG C of roasting 4h are warming up to, tabletting, granulation, the particle for screening 40~60 mesh obtain 10%
Ni- glycine/Al2O3Catalyst.
Embodiment 8
A kind of preparation method of methane dry reforming nickel-base catalyst, substantially the same manner as Example 1, difference is:
In step (1), Ni (NO3)2·6H2O dosage is 0.26g (0.00089mol, molecular weight 290.81g/mol),
Citric acid (C6H8O7·H2O) dosage is 0.19g, i.e. complexant and Ni (NO3)2·6H2The molar ratio of O is 1:1, SiO2With Ni
(NO3)2·6H2The molar ratio of O is 19:1；60 DEG C of reaction 48h in air-tight bottle；
In step (2), 300 DEG C of roasting 5h are warming up to, tabletting, granulation, the particle for screening 40~60 mesh obtain 5%Ni-
Citric acid/Al2O3Catalyst.
The nickel-base catalyst prepared to the embodiment of the present invention 1~8 and comparative example 1 has carried out methane dry reforming preparing synthetic gas
Reactivity worth evaluation, specific experiment situation are as follows:
0.10g nickel-base catalyst (catalyst is diluted with the quartz sand of 5 times of volumes) is placed in fixed bed reactors,
It is passed through the H that volume ratio is 20% in atmospheric conditions2/N2, total flow 50mLmin-1, with 4 DEG C of min-1Heating rate
700 DEG C are risen to from room temperature, reductase 12 .0h.
Then, H is closed2, continue to be passed through N2, with 2 DEG C of min-1Heating rate be warming up to 750 DEG C, after temperature stablize after,
It is switched to reaction gas (CH4With CO2Volume ratio be 1: 1 gaseous mixture), CH4With CO2Total amount be 100mLmin-1, in P=
1.0atm, T=750 DEG C, CO2/CH4=1.0, air speed=60000mLg-1·h-1Under the conditions of react, the gas after reaction is by Zhejiang
The chromatograph (chromatographic column is 5A and PQ column) of II type thermal conductivity cell detector of Jiang Fuli GC9720 tests and analyzes, and experimental result is shown in Table 1.
The CH4 production performance of the nickel-base catalyst of 1 embodiment of the present invention 1~8 of table
As shown in Table 1, the nickel-base catalyst prepared by the present invention all has higher methane dry reforming reactivity, CH4
With CO2Conversion ratio be respectively higher than 81% and 90%, complexant is not added and carries out the Ni/SiO for preparing after simply grinding2Catalyst is (right
Ratio 1) after reacting 20h, CH4With CO2Conversion ratio 10.7% and 21.3% are down to by 83.6% and 92.1% respectively.With it is right
Ratio 1 is compared, and significant raising has been obtained using the stability of coordination-polishing preparation nickel-base catalyst, after reacting 20h
CH4With CO2Conversion ratio be held essentially constant.
The catalyst prepared using embodiment 1 has investigated the methane dry reforming reaction service life of the catalyst, by Fig. 3 as representative
It is found that catalyst methane dry reforming reactivity worth with higher, after reacting 100h, CH4With CO2Conversion ratio protect substantially
It holds constant.
It is discussed in detail although the contents of the present invention have passed through above preferred embodiment, but it should be appreciated that above-mentioned
Description is not considered as limitation of the present invention.After those skilled in the art have read above content, for of the invention
A variety of modifications and substitutions all will be apparent.Therefore, protection scope of the present invention should be limited to the appended claims.
Claims (10)
1. a kind of preparation method of methane dry reforming nickel-base catalyst, which is characterized in that this method includes:
(1) by Ni (NO3)2·6H2O, complexant and SiO2Grinding, is fitted into air-tight bottle, reacts in 40~100 DEG C；
(2) step (1) reactant is roasted, is warming up to 300~800 DEG C of roastings, be granulated, screen the particle of 40~60 mesh,
Obtain the nickel-base catalyst that Ni load capacity is 5%~20%；
Wherein, any one of the complexant in citric acid, trimesic acid, urea, glycine and niacin；It is described to match
Position agent, Ni (NO3)2·6H2O and SiO2Molar ratio be 1~6:1:(3~20).
2. the preparation method of methane dry reforming nickel-base catalyst according to claim 1, which is characterized in that in step (1)
In, the milling time is 30min.
3. the preparation method of methane dry reforming nickel-base catalyst according to claim 1, which is characterized in that in step (1)
In, the reaction time is 10~48h.
4. the preparation method of methane dry reforming nickel-base catalyst according to claim 1, which is characterized in that in step (2)
In, the calcining time is 3~5h.
5. the preparation method of methane dry reforming nickel-base catalyst according to claim 1, which is characterized in that in step (2)
In, the heating rate is 5 DEG C/min.
6. a kind of methane dry reforming nickel-base catalyst, which is characterized in that the catalyst is by Ni (NO3)2·6H2O, complexant
And SiO2Cross what 40~60 meshes obtained after grinding, sealing 40~100 DEG C of heating reactions, 300~800 DEG C of roastings；Wherein,
Any one of the complexant in citric acid, trimesic acid, urea, glycine and niacin；The complexant, Ni
(NO3)2·6H2O and SiO2Molar ratio be 1~6:1:(3~20)；Ni load capacity is 5%~20% in the nickel-base catalyst.
7. methane dry reforming nickel-base catalyst according to claim 6, which is characterized in that the catalyst passes through such as claim
The preparation method of methane dry reforming nickel-base catalyst described in any one of 1-5 obtains.
8. methane dry reforming nickel-base catalyst according to claim 6, which is characterized in that the catalyst is to pass through Ni
(NO3)2·6H2O, citric acid and SiO2Sieving obtains after grinding, heated sealed reaction, roasting；Wherein, the lemon
Acid, Ni (NO3)2·6H2O and SiO2Molar ratio be 2:1:8~9.
9. methane dry reforming nickel-base catalyst according to claim 6, which is characterized in that the catalyst is to pass through Ni
(NO3)2·6H2O, glycine and SiO2Sieving obtains after grinding, heated sealed reaction, roasting；Wherein, the sweet ammonia
Acid, Ni (NO3)2·6H2O and SiO2Molar ratio be 4:1:8~9.
10. a kind of purposes of the methane dry reforming nickel-base catalyst as described in any one of claim 6-9, feature exist
In the catalyst is reacted for catalytic methane dry reforming preparing synthetic gas.
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